Novel fragrance compositions

ABSTRACT

WHEREIN R1 is hydrogen or lower alkyl, R2 is hydrogen or lower alkyl, and n is 1 or 2; lower alkyl acetals thereof, lower alkylene cyclic acetals thereof and mixtures thereof.   Novel fragrance compositions comprising aldehydes having the structure:

United StatesPatent 1 Hall [ 1 Feb. 13,1973

[ 541 NOVEL FRAGRANCE COMPOSITIONS 75 Inventor: John B. Han, Rumson, NJ.

[73] Assignee: International Flavors & Fragances Inc., New York, NY.

[52] US. Cl.... ...252/522, 424/333 [51] Int. Cl. ..A6lk 27/00 [58] Field of Search ..424/333; 252/522 [56] i References Cited OTHER PUBLICATIONS I Beilsteins l-landbuch' der Organische Chemie Vol. VII

Primary Examiner-Stanley J. Friedman Attorney-Arthur L. Liberman and Harold Haidt s1 ABSTRACT Novel fragrance compositions comprising aldehydes having the structure:

Bl Ra H wherein R is hydrogen or lower alkyl, R is hydrogen or lower alkyl, and n is l or 2; lower alkyl acetals thereof, lower alkylene cyclic acetals thereof and mixtures thereof.

5 Claims, No Drawings NOVEL FRAGRANCE COMPOSHTIONS This application is a division of applicant's parent application Ser. No. 874,038 filed on Nov. 4, 1969 now U.S. Pat. No. 3,636,113 issued Jan. 18, 1972. BACKGROUND OF THE INVENTION There is a continuing search for materials having desirable fragrances. Such materials are sought either to fortify weak natural materials, to obviate weaknesses of natural materials, or to provide new fragrance or perfume types which have not heretofore been available. Such substances desirably have stability in a wide variety of perfumed articles and perfume compositions, are easily manufactured and have intense aromas.

It is known to carry out a two-step reaction wherein myrtenol is reacted with methyl vinyl ether in the presence of mercuric acetate as a catalyst in order to obtain the vinyl ether of myrtenol; and wherein the resulting vinyl ether is then rearranged to form an aldehyde having the structure:

cmo

The compound so formed is relatively uninteresting from the standpoint of perfumery (See Julia et al. Bull. Soc. Chim., 1962, 19471952).

Furthermore, it is known to react nopol (pinomethanol) with phosphorous pentachloride to form a compound of the structure:

then to form the corresponding Grignard reagent from the nopol derivative using magnesium and react the Grignard reagent with triethoxy methane to form 6,6'

dimethyl bicyclo[ 3.1 l ]hept-2-ene-2-propanal (hereinafter referred to as pinoacetaldehyde) having the structure:

./0 cmcmo l THE lNVENTION The invention comprises the novel products, the novel processes and steps of processes according to which such products are manufactured, as well as the use in perfumery of the said novel products and known lower homologues thereof, specific embodiments of which are described hereinafter by way ofexample and in accordance with which it is now preferred to practice the invention.

Briefly, the present invention provides the novel pinane derivatives, alpha-alkyl and alpha, alpha-dialkyl-6,6 dimethyl bicyclo [3.1.1 ]hept-2-ene-alkanals,

wherein R is hydrogen or lower alkyl; R is lower alkyl, and n is 1 or 2 as well asthe corresponding lower alkyl acetals having the structure:

wherein R and R are the same or different lower alkyl groups, and wherein n is l or 2 and lower alkylene cyclic acetals having the structure wherein R is lower alkylene, The invention also contemplates perfume and fragrance materials containing such compounds, as well as the known lower homologues thereof. The materials found'to be useful in the instant invention are produced by several novel methods:

1. One such method involves reacting pinocarveol with a substituted or unsubstituted ethyl vinyl ether in the presence of a protonic acid such as phosphoric acid with or without a suitable additional inert reaction vehicle. When ethyl vinyl ether is used, the reaction product is pinoacetaldehyde. When the vinyl group is alkyl or dialkyl substituted in the beta-position, the reaction product is one of the novel products of this invention. The reaction can be represented as follows:

+ CzHaOC=C The resulting Schiff base is reacted with a Grignard re agent such as methyl magnesium chloride and reacting the resulting salt with a myrtenylhalide such as myrtenyl chloride, myrtenyl bromide, or the like, thus:

The resulting Schiff base, a novel chemical compound, is then hydrolyzed in situ (preferably using an aqueous acid such as 10% sulfuric acid) to form he desired pinoacetaldehyde, or alpha-substituted or alpha, alphadisubstituted pinoacetaldehyde. The general technique applied to alkylation of aldehydes is disclosed by Stork and Dowd at 85 J. Am. Chem. Soc. 2l78-2l80 [July 20, 1963]. The acetals and cycliacetals of the aforementioned aldehydes, again, may be formed as desired as above. It will be understood from the present disclosure that some of the alpha-monoalkyl and alpha, alpha-dialkyl pinoacetaldehyde compounds, can be obtained in more than one stereoisomeric form and that these stereoisomers are intended to be included in the formulas shown.

It has been found that the known pinoalkanals and the novel alpha-substituted and alpha, alpha-disubstituted pinoalkanals and their lower alkyl acetals and lower alkylene cycliacetals of this invention possess a fresh, green aroma, part woodsy, part flowery, ozonelike and reminiscent of early morning dew-laden vegetation. The lower homologs (e.g. the pinoacetaldehyde and pino'propionaldehyde and their lower alkyl acetals) are more pungent and the higher (erg. pinoisobutyraldehyde) unexpectedly softer and more floral; all exhibiting good persistence. This fragrance quality particularly makes pinoalkanols including the novel alpha-alkyl and alpha, alpha-dialkyl pinoalkanals and their acetals and cyclic acetals suitable or incorporation into perfume compositions and fragrance modifying compositions wherein a fresh air fragrance character is desirable. The intensity and other properties of pinoalkanals including the novel substituted pinoalkanals and acetals of this invention are sufficiently marked so that they can be employed either as purified materials or in admixture, or in mixtures of lesser purity as obtained by the novel reactions herein described.

Several pinoalkanals including the novel alpha-alkyl and alpha, alpha-dialkyl pinoalkanals may be conveniently produced from the known material pinocarveol which latter material can be obtained by the process described in the United States application of Peter W. D. Mitchell, Ser. No. 732,539 filed on May 28, 1968, in which beta-pinene is reacted with hydrogen peroxide and a smallamount of selenium dioxide.

One of the reactions of this invention involves a conversion of pinocarveol to yield substantial quantities of the substituted or unsubstituted pinoalkanals. The reaction is carried out with the substituted or unsubstituted alkyl vinyl ethers in he presence of a protonic acid. 7

The reaction product formed is dependent upon the particular substituted alkyl vinyl ether of the formula ART where A is lower alkyl, R is hydrogen or lower alkyl and R is hydrogen or lower alkyl. The following alkyl vinyl ethers will yield the indicated reaction products:

REACTlON PRODUCT 6,6 dimethyl bicycle [3.1.1]

hept-2-ene-2-propionaldehyde ALKYL VINYL ETHER ethyl vinyl ether ethyl (Z-ethyl-l-butenyl) ether ethyl (Z-methyll -pentenyl) alpha,6,64rimethyl-alpha-npropyl-bicyclo [3.1.1 ]hept-2- ene-2-propionaldehyde. ether The preferred protonic acid phosphoric acid. In order to effect the reaction, from 0.005 percent up to 2 percent and preferably from 0.01 percent up to about 0.5 percent (by weight of the reaction mass) of protonic acid should be used. The reaction is preferably carried out at superatmospheric pressures. The best results have been obtained with reaction pressures in the range of from about three to about seven atmospheres and temperatures in the range of l40-l 7 0C. The amount of reactants used can vary over wide limits, and preferably the alkyl vinyl etherreactant is present in excess. Preferably, the molar ratio of ether to pinocarveol is from 1.511 up to about 2.5: 1. At the termination of the reaction which may proceed for a period of from 1 hour up to 3 hours (depending on the temperature of reaction and the yield desired), the excess vinyl ether reactant is stripped off and the substituted or unsubstituted pinoacetaldehyde is distilled usually under reduced pressures. This first reaction sequence is preferred for the production of unsubstituted pinoacetaldehyde.

A second reaction sequence may also be used for the production of several pinoalkanals. This method can'be practiced step-by-step as follows:

1. Production of the Schiff base of an aldehyde In producing the Schiff base, any aldehyde may be used which has an available a-hydrogen and any primary amine can be used. Thus, in producing pinoisobutyraldehyde, for example, the aldehyde used would be isobutyraldehyde. In producing pinoisopropionaldehyde, the aldehyde used would be propionaldehyde. In production of the Schiff base, the use of equimolar amounts of amine and aldehyde is desirable; use of an excess of either ingredient giving rise to unnecessary added cost. Preferably the temperature of reaction is from C. up to 30C.

2. Production of a Schiff base-Grignard Reagent After drying, the Schiff base produced in (l is reacted with any convenient, inexpensive, readily available Grignard reagent, preferably a lower alkyl magnesium halide such as methyl magnesium chloride in the; presence of a suitable inert solvent such as tetrahydrofuran. The quantity of the methyl magnesium chloride or other Grignard reagent should be in slight molar excess to insure completion of the reaction. The preferred excess of Grignard reagent is of the order of 5-10 percent. The reaction should take place at a temperature in the range of from about 50C to about 80C.

3. Addition of the myrtenyl moiety and hydrolysis At the completion of the reaction of (2), myrtenyl chloride or myrtenyl bromide is added to the Schiff base-Grignard material so produced. It is preferred that the myrtenyl halide be in molar excess with respect to the Schiff base-Grignard material. This reaction is carried out preferably at atmospheric pressure. The preferred temperature range for this reaction is from about 50 to 80C. The product is the Schiff base of the desired substituted or unsubstituted pinoacetaldehyde. The Schiff base so produced is hydrolyzed in any suitable readily available aqueous acid, such as 10% sulfuric acid in order to form the desired substituted or unsubstituted pinoacetaldehyde. The products of the forego- 4O The substituted and unsubstituted pinoalkanals and corresponding acetals of this invention can be incorporated into a wide variety of compositions which will be enhanced by their flowery, ozone-like, woodsy notes. As noted above, the novel materials, as well as The term perfume composition" is used herein to mean a mixture of compounds, including, for example, natural oils, synthetic oils, alcohols, other aldehydes, ketones, esters, lactones, and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain: (a) the main note or the bouquet or foundationstone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which 7 include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and (d) top-notes which are usually low-boiling fresh-smelling materials. Such perfume compositions or the novel materials of this invention can be used in conjunction with carriers, vehicles, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants, and the like.

In perfume compositions the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of the each ingredient. Thus, the substituted and unsubstituted pinoacetaldehydes and acetals thereof of this invention can be used to alter the aroma characteristics of of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient of the composition. v

The amount of pinoalkanal or alpha-substituted and disubstituted pinoalkanals or acetals thereof of this invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 3.0 percent by weight of mixtures or compounds of this invention, or even less can be used to impart a fresh air flowery odor to soaps, cosmetics and other products. They are well suited to use in the preparation of lavender fragrances. The amount employed will depend on considerations of cost, nature of the end product, the effect desired in the finished product, and the particular fragrance sought. All parts, proportions, percentages, and ratios herein are by weight, unless otherwise indicated.

the known pinoacetaldehyde and pinopropionaldehyde, can be added to perfume compositions in the pure form or in admixture with one another. They can be added to mixtures of materials in fragrance-modifying compositions to provide a desired fragrance character to a finished perfume material or other article. A fragrance-modifying composition is one which does not of itself provide total fragrance impression (as would a perfume composition), but it alters and enhances, reinforces or fortifies another composition 60 to provide a finished perfume or overall fragrance.

The perfume and fragrance compositions obtained according to this invention are suitable in a wide variety of perfumed articles and can also be used to enhance, modify or reinforce natural fragrance materials. It will thus be appreciated that pinoacetaldehyde, pinopropionaldehyde and substituted pinoalkanals, and acetals thereof of this invention are useful as olfactory agents and fragrances.

The substituted or unsubstituted pinoalkanals o acetals disclosed herein, mixtures thereof, and reaction mixtures containing them can be used alone, in a fragrance-modifying composition, or in a perfume composition as an olfactory component in detergents and soaps; space deodorants', perfumes; colognes; bath preparations such as bath oil, bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, sun screens; powders such as talcs, dusting powders, face powder and the like. When the pinoalkanals or acetals of this invention are used in perfumed articles such as the foregoing, they can be used in amounts of 0.1 percent or lower. Generally it is preferred not to use more than about 1.0 percent in the finished perfumed article, since the use of too much will tend to unbalance the total aroma and will needlessly raise the cost of the article.

The following examples serve to illustrate embodiments of the invention as it is now preferred to practice it. It will be understood that these examples are illustrative and the invention is to be considered restricted thereto only as indicated in the appended claims.

EXAMPLE I Preparation of Pinoacetaldehydc by Reaction of Pinocarveol with Ethyl Vinyl Ether Into a l-liter autoclave the following ingredients were placed:

250 g. pinocarveol 250 g. ethyl vinyl ether 0.5 g 85% phosphoric acid The contents of the autoclave were heated at a temperature range of l50l55C over a period of 2% hours. The pressure within the autoclave was in the range of 70-80 psig. At the termination of the reaction the contents of the autoclave were removed and the organic phase was washed with an equal volume of percent of sodium bicarbonate and then with an equal volume of water. The excess ethyl vinyl ether was stripped off and the resulting crude product was distilled at 8488C on a 12 inches Goodloe column (pressure: 2.8-3.2 mm Hg; reflux ratio 9:1). Infra red, NMR and mass spectral analysis confirmed the following structure of the product:

CHzCH1C\ I H The pinoacetaldehyde thus formed had a highly persistent, very fresh, pungent, flowery, woodsy, ozonelike odor reminiscent of early morning dew-laden vegetation.

EXAMPLE II The Preparation of Pinoisobutyraldehyde a. Formation of Schiff base 396 g. (4.0 moles) of cyclohexylamine was placed in a lflask. Over a period of 1 hour, while maintaining the temperature at C, 292 g. of isobutyraldehyde was added. At the end of the addition period, the aqueous and organic phases were separated and the organic phase consisting of the Schiff base N(2-methyl propylidene) cyclohexylamine was dried over magnesium sulfate and distilled at a vapor temperature of61-67C (pressure: 13-14 mm Hg);

b. Reaction of Schiff base with Grignard Reagent Into a 3-liter flask purged with nitrogen, 680 ml. (2.02 moles) of methyl magnesium chloride in tetrahydrofuran was added. The contents of the flask were heated to 60C. Over a period of 1 hour, 282 g. of the Schiff base produced in Part (a) was added, maintaining the-temperature in the range of 50 70C. After addition, the contents were heated for 4 hours until the evolution of hydrogen ceased;

c. Reaction of the Schi ff base Grignard Reagent with Myrtenyl Chloride Over a period of 2 hours 444 g. of 71.3 percent (wt.) myrtenyl chloride were added -to the reaction product produced in Part (b), while maintaining the temperature in the range of 65 70C. After addition was completed, the reaction mass was stirred for a period of 8 hours, maintaining the temperature in the range of 72C;

d. Hydrolysis of Schiff base product formed in (c) The pH of the reaction mass was brought to 4 by addition 1,140 g. of 10 percent aqueous sulfuric acid. The mass was then heated for a period of 30 minutes at C after which the aqueous phase was separated from the organic phase. The aqueous layer was extracted with 550 ml. of toluene and the toluene extract was bulked with organic layer. The organic phase was then washed per the following sequence:

a. One 550 ml. volume of 5% aqueous hydrochloric acid;

b. One equal volume of saturated sodium chloride solution;

c. One equal volume of a 3% sodium bicarbonate solution (bringing the pH to 8.0);

d. One equal volume of a saturated sodium chloride solution [bringing the pH to 7.0]. The solvent was then stripped off and the reaction product was distilled in a 12-inch Goodloe column at a vapor temperature of 9l94C [pressure:2.6-3.0 mm Hg.:reflux ratio 9:1]. 236 g. of the reaction product, alpha-pinyl isobutyraldehyde was recovered, the structure of which, confirmed by NMR, Infra Red and Mass Spectral analysis was as follows:

The alpha-pino-isobutyraldehyde had a highly persistent, fresh, soft floral, woodsy, ozone-like odor reminiscent of early morning dew-laden vegetation.

EXAMPLE Ill The following mixture is prepared:

Parts by Weight Ingredients Coumarin 200 Linalol 50 Benzylacetate 30 Geranium absolute 50 Methylacetophenone 40 Bergamot Lavander, Barreme 80 Pinoacetaldehyde (Product of Ex. 1) 25 Benzophenone 25 Trichloromethyl phenyl carbinyl acetate 20 Hydroxycitronellal 2O Sauge Sclaree 20 Neroli bigarade l0 lsobutylsalicyclate 10 Ylang-Ylang Bourbon l0 Patchouli Oil 5 Vetiver acetate 5 Mousse de Cherie absolute l0 Anis alcohol 5 Basilicum absolute A pleasing new fragrance results giving an interesting variation which can be described as a fresh-air quality to the basic classic Foin Coup cologne blend.

EXAMPLE iv The following mixture is prepared:

Parts by Weight Ingredient lOO Coumarin 200 Linalool 50 Benzylacetate 3O Geranium absolute 5O Methylacetophenone 40 Bergamot l Lavander, Barreme 8O alpha-Pinoisobutyraldehyde (Product of Ex. ll)

Benzophenone 25 Trichloromethyl phenyl carbinyl acetate 20 Hydroxycitronellal 20 Sauge Sclaree 2O Neroli bigarade l0 lsobutylsalicylate l0 Ylang-Ylang, Bourbon 10 Patchouli Oil 5 Vetiveryl acetate 5 Mousse de Chene absolute l0 Anis alcohol 5 Basilicum absolute A pleasing new fragrance results giving an interesting variation which can be described as a fresh-air quality to the basic classic Foin Coupe cologne blend.

It will be appreciated from the present description that the pinoalkanals and the novel substituted derivatives of pinoalkanals and acetals thereof can be included in other perfume compositions and in other perfumed articles such as detergents, shampoos, powders, soaps, deodorants, sachets, paper goods, and the like.

What is claimed is: I

l. A perfume composition comprising (1) an effective perfurning amount of a bicyclic compound selected from the group consisting of 6,6-dimethyl bicyclo [3.1.1.] hept-2-ene-Z-propionaldehyde, 6,6 dimethyl bicyclo [3.1.1.] hept-2-ene-n-butyraldehyde and a,a,6,6b-tetramethyl bicyclo [3.1.1] hept-2-ene-2 propionaldehyde; (2) a material selected from the group consisting of a natural perfume oil and a synthetic perfume oil; and (3) at least one adjuvant selected from the group consisting of alcohols, aldehydes, ketones, esters and lactones.

2. The perfume composition of claim 1 wherein the bicyclic compound is a,0z,6,6-tetramethyl bicyclo [3. l .l hept-2-ene-2-propionaldehyde.

3. A perfumed article comprising an effective perfuming amount of the perfume composition of claim 1 and a detergent, soap, bath preparation, hair preparation, cosmetic preparation or powder.

4. A perfumed article as defined in claim 3 wherein the bicyclic compound, is a,a,6,6-tetramethyl bicyclo [3.1 l hept-2-ene-2-propionaldehyde.

5. The perfume composition of claim 1 wherein the bicyclic compound is 3 percent of the weight of the entire composition. 

1. A perfume composition comprising (1) an effective perfuming amount of a bicyclic compound selected from the group consisting of 6,6-dimethyl bicyclo (3.1.1.) hept-2-ene-2-propionaldehyde, 6, 6 dimethyl bicyclo (3.1.1.) hept-2-ene-n-butyraldehyde and Alpha , Alpha ,6,6-tetramethyl bicyclo (3.1.1) hept-2-ene-2-propionaldehyde; (2) a material selected from the group consisting of a natural perfume oil and a synthetic perfume oil; and (3) at least one adjuvant selected from the group consisting of alcohols, aldehydes, ketones, esters and lactones.
 2. The perfume composition of claim 1 wherein the bicyclic compound is Alpha , Alpha ,6,6-tetramethyl bicyclo (3.1.1) hept-2-ene-2-propionaldehyde.
 3. A perfumed article comprising an effective perfuming amount of the perfume composition of claim 1 and a detergent, soap, bath preparation, hair preparation, cosmetic preparation or powder.
 4. A perfumed article as defined in claim 3 wherein the bicyclic compound, is Alpha , Alpha ,6,6-tetramethyl bicyclo (3.1.1) hept-2-ene-2-propionaldehyde. 